Preparation of hydrogen-carbon oxide mixtures and catalytic reaction thereof



' Dec. 4, 1951 A. BELCHETZ 2,577,563

PREPARATION oF HYnRoGEN-CARBON oxIDE MIxTuREs AND CATALYTIC REACTION THEREOF Filed May 20, 1947 5 Sheets-Sheet l asoman Dc. 4, 1951 A. BELcHETz 2,577,563

PREPARATION OF HYDROGEN-CARBON OXIDE MIXTURES AND CATALYTIC REACTION THEREOF 3 Sheets-Sheet 2 Filed May 20, 1947 farm/AN;

' INVENOR. ARA/ULDBELUHETZ .if am .ATT

A. BELCHETZ PREPARATION OF HYDROGENCARBON OXIDE MIXTURES AND CATALYTIC REACTION THEREOF Z5 Sheets-Sheet 3 Filed May 20. 1947 Patented Dec. 4, 1951 PREPARATION OF HYDROGENa-GARBON- OXIDE MIXTURES ANDy CATALYTIG. REACTION THEREOF Arnold Belchetz, Larchmont, Nl Y., assgnor to The Mi W: KelloggCompany, .Tersey` City, N. JL,

a corporation of 'Delaware ApplicatimMay zu, 1947,y serialNaaasz.

21 Claims. (Cl. 261K-449) This invention relates to the hydrogenation o1.` carbon oxides to produce hydrocarbons having more than one carbon atom per molecule and oxygenated organic compounds. In one` aspect' this invention relates to the hydrogenaton of' carbon monoxide in the presence of a finely divided hydrogenaton catalyst under conditions such that organic compounds are produced'- The process of this invention is applicable also in reacting. hydrogen. with carbon dioxide. In the following description of the invention the hydrogenation of" carbon. monoxide will bei referred' to specifically, It will" b'e understood, however, that the invention, is ofwder application. includingwi'thin its scope the hydrogenatlon otany oxide of'carbon.

It" has been known, for some time that hydrof and, carbon monoxide may be made. to react exothermioally in. the, presence ofi` a. catalyst. under speciiic reactionvcondtionstto form hydrocarbons andoxygenated compounds. In, generah the synthesis. of these. organic, compounds` by the.. liiyldrog,enationv of" carbon monoxide is accomplished'l in the` presence, of a metal" or anN 25 oxide of" a. metal'. chosen from. group VIII? of the. periodic. tahle as a catalyst, at pressures below about. 500" pounds perA square inch gage andat,temperatureshelow about' '750Fy Fi The synthesis feed" gas. or reaction mixture comprisesa mixture. of abouti to Zmol'sofhyd'rogen.. per mol of' carbon monoxide..

An. object.. of.. this. invention .is to. provide an.

improved. process,y for the. synthesis of. organic compounds..

It is also an object of this invention.=topro.. duce a gas rich in hydrogen and an oxide of carbon, such as 1` carlton:V monoxide;

Another object. of` this invention `is to provide an integrated process for the preparation of theieedgas and thesynthesis.oiorganiocomfpounds. therefrom.

Still'another. object ofjthis.. invention. is to provide a` method'. for hydrogenating carbon..

provide a-methodior'controlling thetemperature..

of," reaction in the` synthesis-of` organic.. compounds, the; hydrogenation of. carbon monoxide.. ilet a turtherf object; of thisi intention..- is.L to,

provide av method for the' regeneration of a` partiallyA deactivated catalyst for use inthe hydrogenation of".y carbon monoxide'.

Another objectv of'this` inventionv is' to pro videl a process. for the hydrogenation"of-I marooni monoxide'y hyl the use ofl arela'tively cheap and" inexpensive` hydrogenation catalyst.

Various other objects` and advantages will be'- come apparent to those skilledU in the art froml the accompanyingy description and" disclosure:

It is believed that the invention mayl be best" described by reference to the` accompanying drawings which show at process for the hydrogenation ofi an oxide;` ofv carbonv to produce vorganic compounds. Figure 1 of` the..drawings is a diagrammatic illustration.` in elevation,y partly in cross section, of` an arrangement of apparatus for the synthesis ofl'hydrocarhons with a finely divided hydrogenation catalvstsuspended* in a gaseous reaction mixture. Element- 29 a catalyst oxidizer in whichthe hydrogenationv catalyst is oxidized. Element f6" isLa methane. oxidizer'in` which methane is' oxidized" by' means' of the oxidized catalyst from elementv 29 to produce hydrogen and an oxide ofl carbon. `Ele'' ment 54.: is a synthesis reactorfor the` conversion` of' the hydrogen andthe oxide of' carbon from methane oxidizer IE to organic compounds; Figure 2` of" the drawings is a diagrammatic; illustration in elevation' of.` a modi'cation of. element 29. of Figure 1'.. Figure 3 0'1"the"drawingy is a modification. oi" thev process' and arrange"- ment of apparatus shown in,y Figure 1 andv diagrammatioally illustrates in. elevation an ar'- rangement of apparatus.. partly in` cross section,I for the reactiony between, an oxide of" carbon and' hydrogen tov produce." organic compounds in the presence of," a. nely divided hydrogenation catalyst suspended in a liquid'. Element I`I'3 of Figure 31 represents a synthesis reactor corresponding to elementr Blof Figure 1 hutin which the. finely divided hydrogenation catalyst. is suspended in a liquid.; rather than a gas. The`v use of. catalyst oxidizer29 and methane oxidizerf Hiv is contemplated for 'the preparation of the catalyst. andthe gaseous feed stream to synthesis.`

In Figure 1. of. the. drawings,. pure.- methaneg or. a.methane-containingV gasfrom any suitable source., suchasnatural gas.r or petroleum re'nery wastegases, passes continuously through conduits 9y and M: to, a preheater. 33'., which com.-

prises a .singlevv or series. of conventional' heat..

exchangers and/or gas.. fired'. furnaces` for pre.,- heating. the. methane-containing stream. to` a U temperature of about 800 F. to about 1'700 F., and thence to methane oxidizer I6 comprising an elongated cylindrical chamber internally insulated with refractory material. A finely divided solidcatalyst comprising an oxide, such as an oxide of iron or other metal oxide, at a temperature of about 1850 F. is introduced from conduit I2 into the gaseous stream in conduit I4 and is carried thereby to methane oxidizer I6. Fresh metal oxide may be introduced into the system through conduit II when and if necessary. A gaseous mixture compris- 'ing methane passes upwardly and continuously through reactor I6 at a velocity suicient to suspend, in the preferred embodiment, the metal oxide in a pseudo-liquid luidized condition in methane oxidizer I6 whereby the metal oxide particles attain a high degree of turbulencev inl a pseudo-liquid dense phase of finely divided solids. In the formation of the pseudo-liquid dense phase of metal oxide in` reactor I6, an interface designated as I1 exists between the pseudo-liquid dense phase and a so-called upper dilute phase. A very small amount of entrained catalystris present in the dilute phase, usually less than about 0.01 pound of solid per cubic foot of gas. In methane oxidizer I6 methane is converted to an oxide of carbon and hydrogen as exemplified by the following typical reaction equations for iron oxides:

Generally, the temperature of methane oxidation Vzone I6 will be between about 500 F. and about 1700 F. and the actual operating temperature will depend upon such factors as the composition of the eiiiuent desired and theparticular metal catalyst used. Y

The reactions of the metal oxides with methane to produce hydrogen and carbon monoxide or carbon dioxide are equilibrium reactions each of which reactions are favored by certain conditions of temperature. At relatively high temperatures within the ranges disclosed, the production of carbon monoxide and hydrogen is favored. At relatively low temperatures within the ranges disclosed, the production of carbon dioxide and water is favored. At substantally all temperatures both carbondioxide and carbon monoxide as well as water will be present to some extent in the eiuent from the methane oxidation zone. Therefore, the temperature employed in the methane oxidation zone will often be determined by the amount of carbon dioxide permissible in the synthesis feed gas.

The metal oxide catalyst may be present in any one of several forms, suchv as FeO, FezOa, and FeO'4, and the reaction of the metal oxide with methane reduces the catalyst to a lower oxide or to the elementary metal; under the preferred operating conditions and when using an iron-containing catalyst the iron oxide is reduced to the elementary iron. When using an iron oxide as the source of oxygen, the temperature of reaction in'methane oxidizer vI6 is between about 1100 F. and about 1700 F., for example about 1650 F.- when it is desired to produce carbon monoxide and hydrogen as the main products of the eiiiuent. Temperatures of reaction in methane oxidizer I6 above about 1'700c F. (and in catalyst oxidizer 29 aboverabout 2000 F.) -are undesirable in most instances because of the proximity to the welding temperature of products of reaction of the methane `with the finely divided oxide in oxidizer I6 of between about 10 and about 60 seconds is suflcient, preferably between about 15 and about 30 seconds, when employing a ferruginous catalytic material. The velocity of the upwardly flowing methane containing stream is between about 0.5 and about 6 feet per second, preferably about 1.5 feet per second, when the metal oxide or metal is maintained in the pseudo-liquid fluidized condition. A pressure from about atmospheric to about 500 pounds per square inch gage is appropriate, preferably the pressure is between aboutO and about 300 pounds per square inch gage and will correspond substantially to the pressuremaintained in synthesis reactor 54` and catalyst oxidizer 29. When converting methane with an iron oxide catalyst, a pressure of about pounds per square inch gage is generally employed.

The presence in the catalytic material of minor proportions, usually between about 0.1 and about 5.0 Weight per cent, of promoters, such as copper, manganese', or an alkali metal or alkaline earth compound is recommended in order to promote the oxidation of methane and also because of their beneficial effect in the subsequent hydrogenation of carbon monoxide in reactor 54.

Since the oxidation of methane is endotherrnic, heat must be `supplied to the methane oxidation reaction in oxidizer I6. vNecessary heat is supplied to the methane oxidation reaction according to this invention from the sensible heat of the solid Imaterial from catalyst oxidizer 29 and by preheating the methane feed stream. `'I'he application of the source of heat supply to oxidizer I6 will be more fully discussed hereinafter.

When the methane-containing stream in conduit I4 contains carbon dioxide, which may accompany the methane in conduit 9 or` may be introduced into conduit 4 as a component of the recycle gas from conduit 86, the carbon dioxide may react with methane in the presence of the metal oxide to produce carbon monoxide and hydrogen in accordance with the following typical equation:

.catalyst resulting from the reduction of the metal oxide to a lower oxide or the elementary metal. By heat exchange with air in heat exchanger 2|,

the eiiiuent from methane oxidizer I6 is rapidlycooled to a temperature of about 1000 F. or lower,

preferably to about 600 F. Cooling or quenching f. of the etuent as rapidly as possible isY highly desirable when operating at relatively high tern-v peratures in methane oxidizer I6; such as when The reaction eiilul Asa result of the conversion of methaneto l carbonmonoxide and hydrogen, iron oxides, for example,l are `reduced and the reducedl iron oxides inthexform of a lower oxide or elementary iron isi` removed from the dense'phaseof` methane oxidzer I6 through conduit I8: and introduced intosifconduit 21'.. A11-.iis continuously introduced the system.through` conduitlf22 andi=com pressedl by means of `a conventionalcom'pressor "o'r blower .2l and fpassed; through. conduits 124l andr 2S towatalyst oxidiserI 29. which also comprises an `elongated cylindricalechamber of steel. 'Catalyst oxidation' chamber@` is internally insulated with il.E suitable refractoryv material, such as fire clay oualumina, which, refractoryr material mayfbe internally lined with a :relatively thiisheet-o! heat andoorrosion resistant1alloy,suchas Inconel whichvcontainsfabouti nickelfwith 15% chromium: and 5%" iron insolidsolution. At' least a Vportion `oi' the air:l in conduit 26, iv according` to the. preferred. operating technique; is .byepassed through conduit 21` toflheat exchanger 2i to remove atportionoi' the heat` from the eiiluent-i'rom methane oxidizer "|82 and therebyalsolpreheating the -lair to a temperature .asthigh'i as abouttiil" l F. ori 7100. F. A-irv from `preheater 21 is passed through conduit 21 to. conduit .28. lroniconduit Ih'nely divided solid materialcontainingcat Inti and. at a temperature lcorresporuiing approximately .to Ithe rtemperature vprevailing'- `in. reactor W isi picked up by theair passing througflifcon; duit 21"\and' `is carried tolconduit NMa/nd? thence tocatalystoxidizer 29?... In catalystoxidieer y2'!!- the: reduced oxide of` ametal hor; an elementary metal, such as` iron, is ox'idizedftoL a higher oxide ortoan oxide' therein, asthe case maybe. Preterably, when the-metal isviron, afftcmperature between' abouty i200` Fl and' .about SOO'OPFI is maintalned'in catalyst oxldizer; 218-. As inv methane oxidizerf I5',` the solid` material containingV catalyst issuspended' in? an upward'owing stream oi"` air such fthat f a pseudofliquid 'dense` phase of' -n'nely dividedv solid-.material is hiormed therein having an interface S-I between' `the pseudo-liquid dense phase in the lower portion anda" dilute pliase''in;`

the upper portion of reactor'29. The-pressure in catalyst oxidizer 2191 isv between about atmospheric andfil.` pounds per vsquare inchl fgagefan'd will` generally correspond to thee-'pressure in methane oxidlilerldand synthesis'-reactor EIL i Y l Alslpreviously discussedi. the` finely *divided solids` comprising.' ay metallic-1 loxide' is withdrawn fromy catalyst voxidizer 291..` through stiamdpipel t2 and introduced:` intoy conduiti Ml through' which the methane' screen` istp'assin'g; .'lrhesolids.` are main tained in a uidized. condition and. vstripped"olii nitrogen in `stand'pipe` I2E by introducing steam;y or recycle gael or other-gas, through conduit i3?? Fresh metallic oxide or'v catalyticmaterialmay be introducednto conduit I2. through` conduit list.

Instead of airsubstantially. pure oxygen or. other'oxidizing.` vgas may' be used for oxidizing` catalytic material` in. catalyst. oxidizer` `2 9 with# out; departing from the" scope?y of? invention'.

Louwes Air; howevorrfisfsthefpreierxechoxidizingffgasvboth y Cottrell precipitator, or other conventional means knownto. those skilledin the art for sep`r mating -thevrnetal oxides from' the gaseousefliuentl' Gasesco'm'pri'sing: nitrogen and .substantially free from. 'entrain'ed nneiyl divided? solidsf'are removed from separatorll' troughrconduit and may be vented toi theatmosphex'e. Separated'solidsi or metal' oxides are collectedfin: standpipe as and introduced;y by gravity into fa.- 'stream of` air owing through. conduit-@diortransferback to cataly'st oxldizerf29,asshown,

The operationfoi. catalyst'oxidizer l2li is similar' in` manyrrespects'to theoperation of'methane oxidizer I'B. From :tnestandpoint'or heat; trans# ici-',woatalystl oxidiuerf` ZBVmust'rb'e oneratedv 'atv-a temperia'tu'rey above'. that uwhich is maintained in the methane oxidizer IE. .When` ironniorweze ampia-f is.` oxidized; heatxia llberatedfandlit' d esirable th at sufficient! `'catalyst abe lcirculated vto absorb this hea-t Within theit'emperature limitsstt for. methane oxidizer' I 6. :ain/ri'fcatalyst'` oxidizer y2S; since, for ymasons fgiven previously: automata ture" of `'about '1650*' iF; would? bef'as high. as neces# sary for' ydesinalble.` in the methane oxidizer; iti@ is unlikely that it'would be necessary to'maintain a temperature of muchtaboverISOmF; in thetf'cataiystl oxldizer. 29; These temperatures-would give a spread. 012200 FL whcliisfusuallyamplo for` heat .absorption andrtransfer purposes: It'is desirable" to maintain the` `temperature :1 the catalyst. oxidizeri zalsvlour` as possible; as meenamcall dimculties' decrease the lower'lthertempra-: ture in.v thel system." sum'cie'nt. solid materiali should be'circulated'` to absorbft'he heat 'avowed in the catalystoxidation betweenithe desired tem'- peraturef levels and sufficient' metal shouldlbe presenty in the catalyst or solid.v material to f abe sono' the oxygeny 'which' isf" required laterv in"v the methane oxidation step; n Forv example;- the heat liberated: in the.vk omda--` tion ofthe lronlfw-lll depend upon the Lcoiiditituti in which the viron enters the oxidizer andonftlw particular oxide which isiormed'in the. oxida tion;"thus,-` iff theironr yis oxidized'` trom metallic? iron to lessvheat would be evolvedthanfif'it were oxidized tcl FesO's, or Feroe. Similarly, more .`nea1:\vouIc1` be evolved if"y they iron-entered the `oxidizerl asl Feov andv was oxidiaed to f F6104' and FeaOs. For operationofthissystem; itis not necessary to x'educ'e'the' ironcompletely..toy metallici iron in methane. oxidizer` IGT. Howeuet; the-preferred conditionsfare such in the metlflltie onidizerV IB` thatthe ironoxide willlien'reduced` completely" or' almost completely to metallic before;y being returned` to catalystsoi-iidizvei'-v 28.11

The "spentl cutalystr whichy is." returned tocaw lyct` oxidizer'fzs" from the synthesisreactorrw and.: spent' catalyst separa'tor:y 63;. will usuallyt'oe inthe form 1ct: tremor: iron carottieffsndtswill also contain-a certain amount of -wax or heavy carbonaoeous material, which material will be removed by oxidation in catalyst oxidizer 29. The oxidation of iron to iron oidde or, of a lower oxide to a higher oxide will be a rapid reaction and it is also probable that at the high temperatures maintained in catalyst oxidizer 29, the carbon on the spent catalyst will be oxidized very rapidly, to l5 seconds average contact time of the gas being ample for both these purposes. The supercial gas velocity will preferably be of the order of about 1 to about 1.5 feet per second, so as to reduce the carry-over of catalyst to the solids separator 31 as much as possible.

A gaseous mixture of the products of methane oxidizer I6 and recycle gas containing entrained hydogenation catalyst is continuously passedthrough conduitv5l, a cooler 52, and conduit 53 to ajconventional upflow type synthesisreactor 54'.: In' cooler 52 the `gaseous mixture, which contains' suspended. hydrogenation catalyst, is cooled to aftemperature of about 600 F. to about 300 F. by indirect contact with a varporizable liquid, such as water. The mol ratio of hydrogen to carbon monoxide of the eilluent of oxidizer I6 is about 2: 1 which corresponds to the ratio -of hydrogen to carbon monoxide produced by the conversion of methane with the metal oxide. This s. ingA thecarbon monoxide spacevelocity by -the volumetric fraction of the chargeA` gas.' repre-f sented by carbonmonoxide. v

Catalyst may be withdrawn continuouslyor intermittently from the pseudo-liquid phase of synthesis reactor 54, such as by means of standpipe 5l, and may be passed to conduit 26 through conduit 58 for regeneration by oxidation, or catalyst may be passed directly to vconduit 5I. In the latter manner, at least a sufficient amount of catalyst is withdrawn from reactor 54 and cooledin cooler 52 such thatv the temperatureof reactionA in Y reactor 54 may be maintained substantially'con-v ratio of hydrogenfto carbon monoxide may be somewhat lower than 2:1 as a result of the conversion of CO2 and methane to carbon monoxide and hydrogen, since hydrogen and carbon monoxide are produced in a mol ratio of about 1:1 in this reaction. The ratio `of hydrogen to carbon monoxide in synthesis reactor 54 may be altered to values above or below the aforementioned ratios by recycling unconverted hydrogen and carbon monoxide, such as through line 86. If desired, also, hydrogen, and/or carbon monoxide may beintroduced into conduit 5I from an outside source (not shown) -without departing from the scope of this invention.

When using a reduced iron catalystin reactor 54 for the conversion of the carbon monoxide and Y hydrogen to organic compounds, a temperature ,maintain the finely divided catalyst Vtherein in a pseudo-liquid condition. Numeral 55 indicates the interface between a pseudo-liquid dense phase and a dilute phase of catalyst in reactor 54 similarto that described with reference to methane oxidizer I6. Y The reaction pressure is between about atmospheric and about 500 pounds per square inch gage, and preferably substantially the same as or lower than the reaction pressure in catalyst oxidizer 29 and methane oxidizer I6. From mechanical considerations, pressures lower than about 250 pounds per square inch gage are desirable, such as 80 or 100 pounds per square inch gage. The space velocity in lreactor 54 is equivalent to a charging rate of at least 1 standard cubic foot of carbon oxide, per hour, per pound oi' synthesis catalyst in the dense phase. At lthe preferred gas velocities and when employing an iron catalyst, the minimum space velocity may be defined as 100 volumes of carbon monoxide (measured at standard conditions), per hour, per volume of the dense phase of catalyst when fiuidized in the fresh condition. The absolute space velocity of thecharge gas is determined by dividstent. In other words, suilicient sensible heat is removed from the catalyst in cooler 52 to at least partially compensate for the exothermic heat of reaction in reactor 54; 'y Y V If insufficient` catalyst is supplied toxreactor54 inthe -synthesis gasstream passing through con', duit I9fto conduit 5I, additional catalytic-mwy terial may be withdrawn continuously 'orinter mittently directly from the catalyst dense phase of methane oxidizer I Ii'through aco'nduit or standa pipe 60 and introduced by gravity into conduit 5I When catalyst is introduced into conduit :5l through conduits 60 and 51,the quantity of synthesis feed and recycle gas passing through line 5I may be insumcient to maintain a velocity `suf' cient to suspend or entrain the catalystY and pass the catalyst throughcooler 52. Inorder to eliminate the diilicultyof vcarrying the lcatalyst through conduit 5I and to minimize the tendency of the catalyst or other finely divided solid 'ma'- terial `to agglomerate and settlein conduit 5|.or cooler 52,*'according to a modiI-lcationeof this in` vention, a. vaporizable liquid is introduced into conduit 5I through-inlet conduit55 at a point precedingorfadjacent to the introduction ofthe catalyst from conduits 51'and 60'.' Such a va porizable liquid comprises water or a hydrocar# bon fraction or any suitable liquid which is not detrimental to the hydrogenationreaction under the conditions in 'reactor 54'. A suitableliquid for this purpose is the aqueous condensate recovered as a reaction by-.product Another suitable liquid is a normally liquid hydrocarbon fraction; such as light naphtha fraction boiling in the range between about F. and about 195F. Other normally liquid hydrocarbon fractions comprise either a butane or a pentane fraction or may even comprise an oxygenated organic fraction, such as an alcohol fraction.y vThe injection of'a va-v porizable liquid into Vthe eiliuent in conduit 5| .also aids in cooling the eiliuent to a suiiiciently low temperature prior to entry into reactorl 54.` If sufcient cooling -is effected in this manner cooler 5.2 may be omitted entirely. Y g f Synthesis reaction eiiiuent comprisngorganic compounds, unreacted carbon monoxide and/or hydrogenfand entrained finely divided solids are removed from the upper vportion of synthesis -reactor 54 through conduit 6I and are passedto a catalyst separator 63. Catalyst separator 63 may comprise a cyclone separator or a Cottrellprecipitator or any conventionalmeans forf separating finely divided entrained solids from the reaction eiiiuent. Finely divided catalyst which has been separated from the reactionv eilluent in separator 63 is collected in standpipe 65 and is introduced into conduit 26 for return to catalyst oxidizer 29 where it is re-oxidized. Av portion of the reaction eilluent prior to condensation may be recycled directly through conduit'62 to conduit 5| by means of a compressor or blower (not shown) and thence back to reactor 54. if desired.

substantially to the routlet temperatureiin cone drawn Kor disposal or recoveryoi dissolved roxygenated organic 'compounds condensed `vapors andthe hydrocarbon-rich liquid phase are withdrawn from accumulator 68 'through vconduits FIS and 14, respectively, y'and compression (not shown) are .passed through conduit 1G a l d a conventionalcooler 11 to .a second `lac'ourriula'tor .18 umaintained hat :a

Ihigher than that'existing intreactor 4 Cooler 411 eool's the mixture in 'conduit `1li to Gondensate is extraction, "e phase comprising hydrogen .andfor carbon lmon- Cs hydrocarbons., and :come "G4 from accumulator 18 duit '8-l and lis passed 'to an absorber in `absorber '8"2 the gaseous mixture passes downward lOWng iiquid, such as miner-a1 seal oil, -a't a temperature and a substantially tor A18 under conditions rsuch that substantially ei-1 of "the ccarbcnsla're 'ion oil. The stripped absorptionoili's absorber B2 through conduit 118B. A g ture 'comprising unreac'ted hydrogen or monoxide, or 1moth, together with thii'e, i'

and thane `I`s removed from absorber `82 conduit 8B and according to .a modiaide-mimaintaimne :the temperature in catalyst `copper oxide and `iron or an Fmridi'ae-r 2'9 at-tl'xedesired levelnand ,zprovidesvan eiectivemeans for utilizing excess recycle ses by recovering'its heating value. When :starting up a substantial portion of the methane stream Imust be hurneci` 1n combustion ycheminer ycatalytic `material in 29 vto the `desired temperature. ii/Ietifia-ne.v may be vrintroduced into combuson lchamber 9i yby bye'passingaipo'rtionfof the methane feed in conduit v`9'throueivcenduit88 tocan-- duit I87|, the 4catah'tic material in Ionidizer gto. the :desired temperature, ft frecycie gescand/or methane Iburned in combustion vIch 'mbernl lmay bereduc'ed lor eveneliminated-entirely. Pre'rerably, the rpowdered solid material'used-Ias the catalyst or the-heat `'carrying imateria-lainfthe `various reactionzones initially lthan la minor :proportion by weight'of whose ,particle size greater `than microns. 'Preier'ably., also, `the l greater proportion of v"the soidlmassfco'rnprises ticle size 'issmalier than -100 micronsfincludingiat least y25 weight per centroi the material 1in marthan 40 microns. A highly desirable .powdeied `solid Lmaterial Whichcan cae Vliuiciicecicondi-tienina gaseous mixture fcompnses'at lleast 'T5 percent by weight lthan `1150 microns in `particle t smaller is a `finely v'divided .powder comprising a meta anci/ or metal nitide, fsuch as -r"a l ol the .periodic table, "wlf-uchis "or becomes in the synhesis reaction zone a cataiyst Y the oxide of carbon.

and support lower ox'de or `ce `the elementary metal which is then passed vto reactor 54. Anfoxid'e yof-copper, such G used Ias the oxygen supplying material for the methane I oxidation reaction 1 ably not lower than about 600 may be employed ior rtheoxidation of methane Reduced copperhcontaining GOD m'xture with other as iron ler be used in adricrea thenopoe formatear jsrvetas'tth Amaterial is` removed from methane oxidizer i6 and passed `to cata-f 2,577,563 source of oxygen for the oxidation of methane thesis reactor 54 as a catalyst The use of such in oxidizer I6 and the iron or iron oxide may serve on containing clays as a catalyst is made posas the catalytic material for the hydrogenation sible by the fact that the process of this inveno carbon monoxi e in synthesis reactor 54. on requires either the e of a catalyst contain en operating with a copper oxide at the relang a large proportion of inert material or the tively low temperatures.A it may be unnecessary use of an excess quantity of catalyst as a heat to cool the eiiluent from reactor I6 prior to introcarrier. 'I'he use of such clays as a source of duction into synthesis reactor 54. Copper-concatalytic material constitutes a substantial ecotaining material is recycled from reactor 54 or nomic advantage of the present process over conseparator 63tocatalyst oxidizer 29. l0 ventional processes for the synthesis of hydrooxidizer I 6. 'This is accomplished by passing oxidizer 29,r methane oxidizer I6, and synthesis flnely divided solidl material from catalyst oxidizer reactor 54, at a velocity suilicient to suspend or 29 through conduits I2 and I4 tomethane oxidizer 20 entrain the mass of ineLy divided solids in the and recycle gas in exchanger 33. The amount of pseudo-liquid -condition. However, the velocity actor reactor I6 to urmsh oxygen for the substantial portion of the nely divided solid in oxidation of the methane is relatively small comhe gaseous stream to form a con nuous fluidpared with the amount of solid material which ized soli phase which circulates with the flow must be circulated to furnish heat. This latter 30 ing gas stream without departing from the scope amount will depend to a great extent on the temo 's invention In he former condition the perature differential between reactor 29 and remass of solids may be said to be suspended in actor Is and is at least 5 imes and may be 40 e gas stream bu not entrained or carried which must be cireuiated to supp1y Oxygen, In 35 the mass as such in the direction of flow of the stantially inert material in nely divided form, Cles circulate at a h ra 1n a. statlonar such as alumina, silica, magnesia, bauxite, bento- Pseudo-liquid maSS In 15h18 DSeudO-ll'qllid condini type clays, sand, or other heat earner mation of operation a small proportion of the nel terials desirability of hav' a large pro- 45 divided solids may become entrained in the gasportion of iluent or carrier present in the cata.- @OHS Stream emerging frm the upper surface o1' ic material renders the process suitable for the .the Pseudo llqlll maSS whereby material thus use of cheap natural catalysts which contain entl'aned iS Carried away froln he mass with originally a, major proportion of inactive material. @e emuent gee Such nely dll/1aed Solids Car Such a catalyst comprises a natural montmorilned away With the emuent must be recovered lonite type clay, such as Ittawamba clay, which from theemuent and 1 eeyeled el fresh finely dcontains about 5 weight per cent FezOa and about vided Sonde added t0 the System t0 make UD for 1.3 weight per cent TiOz. A inontmorillonite type the loss by entrammentclay may also be used as a support for impreg- AS Used herein.' 5115961151011 '0f the nely dnated or precipitated catalytic material, since it vided sonde refers to the condltfm ,of the Pass is suitable as a heat carrier and has desirable either when 1t is 1n a Waldo-1111111? COHdlUOD the natural montmorillonite type clay particuthe reaction Z0 larly active as a catalytic agent for the synthesis In the liflefel'led. form 0f the inl/@M1011 With of hydrocarbons, the montmormom'te type clay the catalytic material present in a pseudo-liquid may be treated with hydrogen sulnde under at- Condition. the powdered catalyst mass is mainsure to convert the ferruginous material to the V01ume Occupied by the catalyst mass in the In h lyst is then introduced into the system through 7o the catalyst. The dense phase of the catalyst dlzer I6. If desired, the roasted clay may be recupied by a mixture of gases and powdered cataduced with hydrogen at a temperature of about lyst in which the catalyst concentration is much 1400 F; and lthan introduced ldirectly into syn- 76 lower. and i ummm I3 than theconcentration o! thecatalystr-in l-the dense phase. This diiuse` phase may besaidto be a disengaging zone in which the solids-'lifted above the `dense phase `by thefgas Istream are disengagedf therefrom and Vreturnedtoy the dome phase tothe extent .that such solids-r are present inithe diffuse phase-in excess fof the carrying 'capacity ci the gaststream at the superficial velocity of thel gasstream. This superficial velocityis the velocity at which the gas streamwould `fiori? through the reactor inthe absence of catalyst.

low concentration yof the diffuse phase.,v This zone has theappearance of an interface between two visually distinct phases. l

i Thisoperation ordinarily involves lemployment of catalyst powders and gas velocitiessuchthat 'atreiatively small proportion of the dense fluidiiodtaiyst-mass is `carried away .by entrainmantfandit is necessary, therefore, to provide means in `the reactor for separating such enf trained solids and returning them tothe dense phase, or. to provide means yexternally of the gas reactor to separateentrained solids from the gas streamand return them to thereactor,or other wisc to recover fiinely dividcdsolids` from the product gas stream. r. y n

When` catalyst is permitted to pass out of the reactor by entrainment in the gas stream in either the pseudo-liquid operation or the continuous phase operation, it is necessary to return such catalyst to rthe reactor, or replace it with fresh or revivied catalyst, in order to maintain therdesired volume of fluidized catalyst in thev reaction zone. t. The pseudo-liquid operation in which the iinely powdered catalyst is employed in Ia lform comprisingierruginous material and containing at mostv minor' proportions of promoting agents, such as potassium oxide or other alkali metal` or alkalinoearth compounds,y provides very high concentrationsaoi .solids inthe reaction zone.,k The employment of the ineiylpowdered solids in` a uidized bedwith eiiicient direct or indirect cooling'means also is a factor in permitting a` high ratofof` reaction andconcentration of reactants,`

since itl facilitates' the rapid removal of heat from allwportions of the reaction zone. The pseudoliquid operation, .employing thefinely divided solids, results in concentrations of .solidsof at least about pounds per `cubic foot of therluidined' dense phase, `while the preferred gas'v velocitesfresult in initial concentrations of 40 to 120, or more, pounds per cubic -footofv dense phase. It vwillbe understood that these figures refer `to theinitial average concentration in they-dense phase.` Theaccumulation of reaction `products on 'the solid particles as the operation Aproceeds reduces the densityiof the solids and increases the bulk of thev dense iuidized mass.

The linearvelocity Uof the `gas stream passing upwardlythroughthe ldense phase' is conveniently expresserll initerms of the 'superficial velocity,

which isthe linear velocitythe charge-gas stream `would `assume if passed through the reactorat operating Vconditions inthe absence of catalyst and takes into account the shrinkage in .volume caused by the reaction, and is, preferably, inthe range yo1 from 0.1 .to i6 feetper second. When operating with a continuous catalyst phase 4in which the `catalyst is entrained `in theieflowing gaseous mixture,y velocities as high as y4001"'5() feet per second may be used without departing yfrom the scope of this invention. f

Thetsyn-thesis `reactants are passed "into and through the synthesis reaction zone 54 at espace velocity equivalent to a charging rate of` at least 0.5standard cubic -foot of the carbon oxide, per hou-r, per pound of metal catalyst in the dense catalyst phase. In `the hydrogenation of -carbon monoxide with a catalyst comprising reduced iron, it isfpreferred to operate at aspace velocity lequivalent to a charging rate of atleast- 2.0 standard cubic feet of carbon monoxide per hour, per pound of reduced iron in the densecatalyst phase.v The `charging rate is defined by reference to the carbony monoxide reactant, since the ratio of the hydrogen reactant to the carbon monoxide reactant in the charge gas may vary within wide limits. y i i v -As fused herein, pressures are `expressedas poundsper square inch gage and' volumes are expresse-d as cubic feet at standardl conditions oi F;.and 760 mm. pressure.

According to the preferredv `embodirment of this inventions, synthesis feed'gasicontai-ning hyd-rt `gen and carbon monoxidey in Ia `mol ratio of yabout :2:1 is processed -under vconditions effective to react all or a maior proportion of thef-carbon monoxide, and a portion `of the product-mixture after removal of the greater part of the liquid product, is recycled in a volumetric r-atioto` the fresh feed gals of about0.5:1 to about 10:1,-asa result of which the mol ratio of hydrogen 'to carbon monoxideJi-n the reaction zone itself `may be substantially higher than 251, and as high-as about 5:1 or higher. l f l Itis preferred to operate synthesis reactor 154 at whatever temperature level, in the-rangebf about 350 F. to about 750 is necessaryto eieot high-conversion of `carbon monoxide when treating a `gas charge containing atleast about 1:1 ratio of hydrogen to lcarbon vnionoxdeat a space velocityequivalentto 'a charging rata-"t least about 1-.0 standardtcubic foot "of carbon monoxide, per hour, per pound of iron catalyst n the dense phase. Similarly, it is preferred topp@ crate the methane-foxidzer atwhatever 'tem--l perature level in the range of- 500 F. tol about 1'700a F. is necessary `to 4effect highy `conversion of methane to carbon monoxide and hydrogen; The oxidation ofthe ferruginous material in the catalyst oxidation `zone is carried out `at a's high a temperature as is permissible and at a ten'mera-i which the` reactant gas is passed through 'ther reaction zones at a linear velocity inexcessoll 6 to 10 feet per second, additional meansmust-lbe supplied for removing the bulk of the ycatalyst=or solid material from the reaction efliuent. Thus," a.l settling zone (not shown) "maybe loca'td in conduitsy |79, `32, and 6|, vin which "settling sones the fbulk of the v entrained solidernaterial is sepas* abmes 15 rated from the eiiluent and recycled to therespective reaction zones. Of course, means must still be provided when necessary to remove the small proportion of entrained fine solids after separation of the bulk of the solid material from the eiiiuent, such means being illustrated in Figure 1 by separators 31 and 63. The solids separated in separators 31 and 63 are circulated as previously described and shown.

Since the catalytic material undergoes treatment in catalyst oxidizer 29 at a relatively high temperature, the loss of promoters, such as potassium oxide, from the catalyst by vaporizationv may be considerable, additional promoter may be injected directly into reactor 54 by means not shown. For example, potassium carbonate is `,dissolved in Water and the resulting solution lis injected into conduit I or reactor 54 in an amount suii'lcient to compensate for the loss of potassium promoter from the catalyst in catalyst oxidizer 29. Conveniently, potassium carbonate may be dissolved or suspended in the vaporizable liquid introduced into conduit 5I through conduit 55. The vent gases leaving catalyst oxidizer 29 can be cooled and scrubbed with water to recover the volatilized potassium oxide, which can be returned to reactor 29.

.Although the present invention has been described specically with reference to the oxidation of methane to produce a suitable synthesis feed gas, other hydrocarbons may be oxidized to products, such as carbon monoxide and hydrogen, which are subsequently interacted to form hydrocarbons and oxygenated organic compounds having more carbon atoms per molecule than the feed hydrocarbons. comprise ethylene, ethane, propylene, and propane.

Although the conditions of reaction in the various reaction zones are those which are preferred. using the catalytic materials indicated, other reaction conditions and other catalytic materials may be employed in the process without departing from the scope of this invention.

Figure 2 diagrammatically illustrates a modication of the present invention in which the catalyst is oxidized in a high velocity continuous phase reactor. According to the modification of Figure 2, which will only be discussed briefly,

methane is passed through conduit I4 and heat exchanger 33 to methane oxidizer I6 in a similar manner as described with reference to Figure 1. Finely divided contact material comprising a metal oxide is maintained `in a pseudo-liquid uidized condition in reactor I6 and forms an interface I1 between a lower dense phase and an upper dilute phase of contact material. The methane oxidation eilluent is removed from reactor I6 through conduit I9 and passed through heat exchanger 2| to synthesis reactor 54 of Figure 1. Y

Finely divided contact material comprising reduced catalytic material is Withdrawn from the dense phase of methane oxidizer I6 through standpipe I8. Preheated air from conduit 21 picks up the finely divided contact material from standpipe I9 and the resulting mixture passes to a catalyst oxidation chamber 94 where the reduced contact material is oxidized. Catalyst oxidation chamber comprises an elongated chamber of such kcross sectional area that the velocity of the gases passing therethrough are sufiiciently high that the contact material is carried or entrained in the flowing gases. Section 95 of the reactor 94 comprises a chamber of increased Such feed hydrocarbons cross sectional area for the purpose of allowing' asuicient residence time of catalyst and gases to eect the desired reaction. Section 95, however, is of such size that thev gas is at a velocity sufficient to entrain the contact material therein. The velocity of the upward flowing gases in reactor 94 and reactor 95 is above about 6 feet per second, usually about l0 feet per second, sufciently high such that the so-called pseudoliquid dense phase of finely divided solids is not formed. VThe temperature of reactor 94 is within the ranges. previously disclosed, usually about 1850 F. Additional` heat may be supplied to reactor 94,by passing gases at a high temperature into reactor 94 through `conduit 92 as described with referenceto Figure 1. The oxidation reaction may be accurately and conveniently controlled in reactor 94 by regulating the velocity of the gases passing therethrough, since the residence time of the contact material in reactorvv 94 is a function of the gas velocity. The gaseous mixture containing the entrained oxidized vcontact=material passes from reactor 94 to a separator 96, which may comprise a cyclone separator or other means for separating the entrained contact material from the gases. Separated contact material from separator 96 is collected in standpipe 91 through which it is vreturned to. methane oxidizer I6.

The gaseous eiiluent from catalyst oxidizer `94 is passed from separator 96 through conduit 32, heat exchanger 33, and cooler 36 to a second separator 31. Separator 31 may comprise a cyclone separator or a Cottrell precipitator. Entrained finely divided contact material is separated from the eiiluent in separator 31. The effluent substantially free from solids is vented .to the atmosphere through conduit 39. Separated contact material is returned to reactor 94 through conduits 39 and 26 in a similar manner as described with reference to Figure l.

Additional air may be introduced into reactor 94 through conduit 26. The only mechanical control necessary for regulating catalyst flow between the catalyst oxidation chamber 94 and methane oxidation chamber I6 is a valve on standpipe I9. Instead .of a cyclonevseparator, a water scrubber may be used to remove entrained finely divided solids from the gases in conduit 32. Water containing the solids recovered from the gases in conduit 32 may be returned directly to oxidizer 94 where the water is vaporized.

The vaporized water is condensed from the oxidation eiliuent by means of cooler 36 and is then returned to the scrubber.

Figure 3 of the drawings diagrammatically i1- lustrates a modification of the present Ainvention when the hydrogenation of carbon monoxide is carriedv out at a pressure higher than the pressure existing in methane oxidizer I6 of Figure 1. In this modification the synthesis feed mixture from methane oxidizer I6 of Figure 1 is passed through conduit 5I to a catalyst -scrubber IUI, in which scrubber finely divided entrained catalyst, such as reduced iron, is removed from the feedmixture by Washing or scrubbing the gaseous mixture with a liquid medium introduced into scrubber IIiI through conduit |02. The liquid medium comprises any suitable liquid scrubbing medium which is capable of removing solid material from the gaseous efliuent and is substantially non-reactive with the reactants in the gaseous mixture. Such a medium may conveniently comprise a hydrocarbon fraction recovered as .a product of the hydrogenation reaction. `'Ilae 17 ysynthesis feed gas; which is effluent gas yfrom methane oxidizer. I6 and recycle gas, is usually at a pressure below about 100 pounds per square inch gage when this modiiication is used and must be compressed to a pressure-between about 300 and about 600 pounds per square inch gage. preferably, about 400 pounds per square inch gage. In order to compress the feed gas mixture 'containing hydrogen andv carboni monoxide, 'the untrained catalyst must` be'removed from the feed gas. This is accomplished `in scrubber |0|. Synthesis -feedl gas 'comprising `hydrogen and carbon monoxide in a mol ratio of' yabout y2:1 Iand substantially free from entrainedfcatalyst is removed from scrubberA 'through .conduit |105 land is continuously passed to synthesis reactor |llby'means'ofcompressorlll I. n

scrubber |0| comprises an elongated cylindiical-'chamber having bafflesv or plates |03 therein forl `diverting the flow `of the liquid scrubbing medium and the yupward flowing., gas mixture therein. The scrubbing,A medium introduced through `conduit '|021 in lthe upperv portion of yscrubber'v l|0| continuously passes downward and `eountcrcurrent to the upward flowing, synthesis gas mixture 'and collects in` the lower portion thereotasiindicated bynumeral |04. The liquid scrubbing medium, preferably inthis case `a, hydrocarbon fraction recovered as aproduct of the process, contains substantially all" "of the entrained ycatalyst and is, withdrawn. from` scrubber |0|, through conduit |01. The scrubbing .medium containing thefentrainedk catalyst maybe recycled toi-scrubber |0|` through conduit |08 andzcooler,l |09. `scrubber |0| also cools the synthesis gasy to the desiredtemperature. of vsynthesis reactor H3 or lower. Sensible heat removed `from `the synthesis gas in scrubber |0| by the scrubbingliqu-id is removed by cooler |09 `from the scrubbing liquid prior to reintroduction into scrubber |0|. Fresh scrubbing mediurnmay beintroduced into scrubber |0| through conduit |02', when necessary. A lportion of the scrubbing Inedidiverte'd from conduit-,I 01and passed-through conduits ||0fand H4, andcooler |22, to synthesis reactor |;I3. The. passage of at least aportion of the scrubbing liquid fromscrubber |0| tov synthesis yreactor ||3 supplies make-upvcatalyst in reactor |/l3since thek scrubbing liquid contains 4all of,A the entrained catalystirom the synthesislgas in addition to the catalyst introduced from line 60:. Scrubb'ing medium is introduced into the upper, portion of reactor' I3 through conduitv ||4 and flows downwardA against baffles lllcountercurrent to the upward iowing mixture of hydrogen., and' carbon monoxide. The scrubbing liquidy orhydrocarbon fraction collects in the lowery portion, oi` reactor ||3, as indicated by numeral |.|`1. Thisgscrubbing liquidi or hydrocarbon fraction comprisesthevheavier products of `thegprocesswhich condensein reactor ||3 underz,the.gconditions of temperature and pressure maintained therein. Synthesis feed gas isrin troduced into theliquidphase ||1 of reactor, H3 through conduit |05 ahddispersionmeans ||2 which may comprise'k a suitable perforated con:- dult or nozzles. If desired, a. portion or all of the synthesis gas may 'be' introduced above the liquid, phase through conduit |06; asy shown.

"When introducedy through conduit |06, the synthesis; gasr-is absorbed in the hydrocarbon frac'- tion and the` synthesis reaction is catalyzed by thesuspended catalyst in the liquid.y A tempunture. between aboutv 250 F. and about 50W-F. ill' maintained in-reactor" I3. Forv eiectivevcata- 18 lyzation` -of the 'c :a-rlionv monoxide fand reaction,v the :liquid phase should contain between about 0.5 and about 3 pounds of suspended catalyst per gallon kof liquid, preferably, l pound of suspended catalyst per gallon of hydrocarbon liquid.

Hydrocarbon liquid isremoved from reactor H3 through conduit llfor continuous 'recycling to the upper lportion `of-reactor j||i3r through conduits- |0, H4, and coo1er `|22. Cooler |22'removes sensible heat -from the hydrocarbony liquid `and thereby aids in the control of the temperature-in reactor |13. A portion of the catalyst may withdrawn through yconduit |46 andfpassed to filter |41 in which suspendedgcatalyst isA removed from the liquid medium. Filter |41 comprises any conventional type of separating meansor lter press for separating suspendedsolidsqirom a liquid. Filtered catalyst is removed ffromrllter |41 through conduit IfISl'andv is introduced into catalyst oxidizer of' Figure l by l'means of vconduit 26 through whichair is Iiowing. Catalyst may be introduced into:` conduitf26 by lany suitable means, such yas a stanlpipe or a --Fuller Kinyon pump (not shown). l The catalyst-in vcatalyst oxidizer 29 is oxidized aspreviously discussed with reference to Figure l; andeventuallyitis-recycled with the synthesis feed gas -to freactor ;I |32 A liquid. hydrocarbon fraction substantially `free from suspended catalyst is removed `from liii-ter |47 through conduit |48v and may be recovered as aproduct of the process through-conduit |44. A portion of the -liquimphase |.|1 of reactor ,|18 must be continuously or intermittently withdrawn from the system as; a product of the processsince the quantity of liqu-id in reactor ||3 increases as a result of.. the reaction of carbon monoxide and hydrogen toproduce liquid-hydro,- carbons therein. y

A gaseous effluent is continuously withdrawn from reactor I|3 through .conduit` ||9 andl `is vpassed to an accumulator |24 'after passing through a condenser |23. Condenser |123 `may comprise, any suitable heat exchange or cooling means, either as., a'rlsingle unit or asa seriesjof units. The gaseous eiiluent in conduit ||9 cooled to about 150F. or lower by cooler ,123, preferably to a temperature of about "F. Two liquid phasesl are formed in accumulator A|24 which is at substantially the same pressure as reactor H3; one. liquid -phaseHiZE comprisesa khydrocarbon-rich phase and the other liquid phase I2\'| comprises an` aqueous-rich phase.l At least a portion of ther hydrocarbon-rich liquid phase |2 6 yis removed from accurnulator'lll` through conduitr |28 andk is continuously or intermittentlyA recycled`v to the upper portionofgreactor ||3. In this manner, the `recycled oil yis vaporized which vaporization aids in the control of the reaction, temperature inreactor |I3j. The return of theliquid hydrocarbon phase'frm accumulator |-2`4`also results lin-a substantiall in crease in the' amount of higher boiling hydrocarbons produced` and creates an equilibrium in reactor |I3 in the production of the hydrocarbons represented -by the compositionhof the fraction returned through conduit |28 such that-a minimum amount of relativelyflow boil-ing, hydro', carbons are produced. Ifdesired, a portion of the light hydrocarbons from accumulator |24 may be withdrawn therefrom through conduit |29l andrecoveredas aproduct ofthe `process by a subsequent purification and separation* system (not shown). The "aqueous-rich liquid phase |21 of accumulator |214fislwithdrawnthrough conduit v pounds.

`affilata?,

i9 |3l and may be passed to a conventional separation and purication system (not shown) for the recovery of water soluble oxygenated organic `chemicals, which may comprise valuable products !tion of the liquid phase in reactor ||3 is With- `drawn therefrom through conduit |36 and passed through a conventional cooler |31 to a settler '|38 which is at a slightly higher pressure than scrubber which in turn is at substantially the same pressure as reactor |6 of Figure 1. In settler-|38the liquid separates from the uncondensed gases which are released as a result of the reduction in pressure from reactor ||3 to settler |38. The liquid phase |39 of settler |38 comprises a slurry of solids and liquid organic com- On standing in settler |38, the solids settle to the bottom as a heavy slurry in liquid hydrocarbon and are withdrawn through conduit |42 and introduced into conduit IIO for return to the reactor ||3 through conduits ||0 and H4. Liquid Withdrawn from the upper level of the liquid phase |39 through |43 will be relatively free of suspended solids and is either passed to scrubber |03 through conduit |43 or removed from the system through conduit |44. Uncon- Ydensed gases are withdrawn from settler |38 through conduit |4| and introduced into the synthesis feed gas in conduit |05 for return to reactor ||3. This modification may be omitted, if desired; however, it does comprise a. convenient method for supplying and regulating the cornposition of the scrubbing medium to scrubber |0I.

In the liquid phase `process of Figure 3 the catalyst is substantially the same in composition and in size as that used in the vapor phase process described with reference to Figure l and further discussion thereof is deemed unnecessary. Preferably, the space velocity of the gaseous feed mixture introduced into reactor ||3 is between about and about 250 volumes per hour per volume of catalyst suspended in the liquid medium of reactor ||3.

Although a reduced iron catalyst was speci- 'lcally described in the discussion of Figures l, 2, and 3, another suitable catalyst comprises a cobalt-thoria catalyst. Using a cobalt catalyst in the vapor phase of Figure l, the synthesis reaction is carried out at a temperature below about 450 F. In the liquid phase process of Figure 3, using a cobalt catalyst, the synthesis reaction is carried out at a temperature between about 300 F. and about 450 F., usually at a temperature above about 400 F. In both vapor and liquid phase processes for the synthesis of hydrocarbons, 90 to 100 per cent conversion of carbon monoxide is realized with `the production of high yields of hydrocarbons having more than one carbon atom per molecule and oxygenated organic compounds.

In the operation' of the modification shown in Figure 3, the iiow of liquid through conduit |36 may be maintained constant and the quantity of liquid withdrawn from the system through conduit |46 may be regulated by a conventional ow control valve responsive to the liquid level in reactor ||3 in order to maintain a constant liquid level therein. Alternatively, the amount of liquid withdrawn from the system through catalyst oxidation zone.

conduit |46 may be maintained constant and the amount of liquid flowing through conduit |36 may be responsive to the liquid level in reactor ||3. The rate of circulation 'of liquid through conduit ||4 depends on the amount of heat required to be removed from reactor I3 to control the temperature therein.

Example The following example is offeredas a means of better understanding the present invention, particularly as to the catalyst oxidation step and the methane oxidation step. The example illustrates specic operating conditions for the production of approximately 1,000,000 cubic feet per hour of synthesis feed gas.

Approximately 14,860 pounds per hour of Since the oxidation of methane is an endothermic reaction, approximately 100,100,000, B. t. u.s per hour are required for this reaction which heat is supplied from the sensible heat of the incoming methane and solid material. The reaction eliiuent containing carbon monoxide and hydrogen at a temperature of about 1650 F. is removed from the methane oxidation zone and heat exchanged with the air entering the system. The

heat exchange with the air cools the reaction eliluent from about 1650" F. to about 600 F. with the removal of about 21,570,000 B. t. u.'s of heat per hour. In this manner the air which enters at a temperature of about F. is preheated to about 1435 F. prior to introduction into the Iron oxide and heat carrier material of aiinely divided form are maintained in a pseudo-liquid dense phase condition in the methane oxidation zone at an upward linear gas velocity therein of about 1.5 feet per second.

Approximately 38,910 pounds per hour of iron and approximately 1,802,670 pounds per hour of inert heat carrier material are removed from the methane oxidation zone and passed to the catalyst oxidation zone. This iinely divided solid material removed from methane oxidation zone is at a temperature of approximately 1650o F. and is passed from methane oxidation zone to the catalyst oxidation zone by means of the preheated air. In the catalyst oxidation zone the iron is oxidized with a liberation of approximately 106,500,000 B. t. u.s per hour of heat. The reaction temperature in the catalyst oxidation zone is about 1850 F. The iron is oxidized according to the following typical equation:

3Fe+202=Fe304 A reaction efliuent comprising 48,960 pounds per hour of nitrogen at a temperature of 1850 F. is removed from the catalyst oxidation zone. This eiiluent is heat exchanged with the incoming methane whereby the eiliuent is cooled to a temperature of about 307 F. with a transfer of about 30,450,000 B. t. u.s of heat per hour. The

2l" nnely divided iron-containing material and'inert heat carrier are maintained in a pseudo-liquid uidized condition in the catalyst oxidizer at an upward linear gas velocity therein of about 1.5 feet per second.

Approximately 53,770 pounds per hour of FeaO4 and approximately 1,802,670 pounds per hour of heat carrier material are removed from the pseudo-liquid dense phase of the catalyst oxidation zone at a temperature'of about 1850 F. and introduced into the methane feed stream. The resulting mixture of heat carrier, iron oxide and methane is then transferred to the methane oxidation zone and the cycle is repeated.

Under the above specific conditions of operation, 1,000,000 cubic feet per hour of lsynthesis feed gas is produced containing approximately 26,000 pounds per hour of carbon monoxide and about 3,720 pounds per hour of hydrogen. This gaseous effluent at a temperature oi' approximately 600 F. is then passed to a synthesis reaction zone under conditions suitable for the production of hydrocarbons and oxygenated organic compounds. The eiiluent contains finely divided entrained solid material comprising iron in amounts sufficient to supply the make-up catalytic material for the synthesis reaction zone. The synthesis reaction is effected at a temperature of aboutv 600 F. using a finely divided iron catalyst present in the reaction zone in a fluidized condition. A portion of the catalytic material of the synthesis reaction zone is removed therefrom and passed to the catalyst oxidation zone from where it passes through the system, previously described, and back to the synthesis reaction zone.

Several distinct advantages of the present combination process for the oxidation of `methane and the subsequent hydrogenation of thecarbon monoxide produced thereby should be emphasized. These advantages comprise the use of the same catalytic material throughout `the system for use both as a heat transfer medium and as a catalytic agent for the oxidation of methane and the hydrogenation of carbon monoxide. Another advantage constitutes the useof the catalyst oxidation zone for oxidation of the catalyst for subsequent use in the methane oxidation step and for the regeneration of the used or spent catalyst from the synthesis reaction zone by the removal of carbonaceous deposits therefrom. Still another advantage is found in the accumulation of the heat of oxidation of the catalytic materialfor supplying at least a portionof the heat'necessary to oxidize the methane to a suitable synthesis feed. Such advantages render the present process a highly economical one and makes it adaptable to the use of low grade catalytic materials which otherwise could not be used to advantage in the synthesis of organicI com-l pounds.

Certain valves, coolers, heat exchangers', heaters, pumps. etc., have been omitted as a matter will become obvious to those skil1ed"`in`the art;`4-

consequently, the drawings should not be concontaining gas stream upward through a `first reaction zone in the presence of a finely divided solid material comprising a reducible metal ox-I ide which in its reduced form is active as a catalyst for the hydrogenation of carbon monoxide suspended in said gas stream under conditions such that methane is oxidized to carbon monoxide and hydrogen, maintaining a temperature of reaction in said first reaction zone between about 1100 F. and about 1700* F., withdrawing finely divided solid material comprisingr reduced metallic material from said first reaction zone and passing same to a sec- 0nd reaction zone, suspending said finely divided solid material in` an upward flowing oxygen-containing gas under conditions such that the reduced metallic material is oxidized, maintaining a temperature of reaction in said second reaction zone between about 1200 F. and about 2000 F. and above the temperature of reaction in said first reaction zone, removing finely divided solid material comprising oxidized metallic material from said second reaction zone and returning same to said first reaction zone to supply oxygen for the oxidation of the methane therein, the Weight of said finely divided Solid materiau circulated between seid met and said second reaction zone being at least five times the Weight theoretically required for sup-` plying oxygen for the oxidation of methane such that a major proportion of the heat required in said first reaction zone is supplied from the sensible heat of the solid material circulated from said second reaction zone, withdrawing from said rst reaction zone a gaseous efiluent containing carbon monoxide, hydrogen, and beof convenience and their use and location in the arrangement of apparatus will become obvious to those skilled in the art without departing from the scope of this invention. The size and length of certain conduits of Figures 1`, 2, and 3 `of the drawings are not proportional to the amount of fluid passing therethroughpnor ytliedistance travelled, but are `merely diagrammatinal. It is not intended to limit any particular location as shownv in the drawing, but various. minor modifications' and-alterations', as well as omissions of i certainpieces fof" equipment;

tween about 0.001 and about 0.01 pound per cubic foot of gas of finely divided solid' material comprising reduced metallic material, introducing said gaseous effluent containing said finely divided solid material from said first reaction zone into a third reaction zone, in said third reaction zone reacting hydrogen and carbon monoxide to produce organic compounds, maintaining the temperature of reaction in said third reaction zone between about 350 F. and about 750 F., removing finely divided solid material comprising metallic material from said third reaction zone and recycling same to said second reaction zone, removing from said third reaction zone a gaseous ellluent comprising organic products of the process and separating same from said effluent, maintaining an upward linear velocity of the gaseous streams inthe aforesaid reaction zones between about 0.5 and about 6 feet per second under conditions such that the finely divided solid material is suspended in the upward' flowing gaseous stream in a pseudo-liquid uidized condition whereby the finely divided solids achieve a highly turbulent condition in a pseudo-liquid dense phase, and maintaining the aforesaid reaction zones at substantially the same pressure between about atmospheric and about 500 pounds per square inch gage.

2. The process of claim 1 in which additional -iineiyy divided solidv material is passed directly 3.. The'process of claim 1 in which said finely' divided solid material comprising a reducible metaLoxidei which in its reduced form is active as a catalyst for the hydrogenation of carbon monoxide is a montmorillonite type clay containing iron in an amount effective to promote the reaction of hydrogen and carbon monoxide to produce organic compounds.

4. The process of claim 1 in which said finely divided. solid material comprises in addition to saidireducible metal oxide a finely divided iner-t material.

5. A. process for the synthesis of organicicompounds which comprises passing a methane-containing gas stream upward through a first reaction zone in the-presence of a finely divided solid material comprising a reducible metal oxide which in its reduced form is active as a catalyst for the hydrogenation of an oxide of carbon suspended in said gas stream under conditions such that methane is oxidized to produce hydrogen and an-oxide of carbon, maintaining a temperature of reaction in said first reaction zone between about 500 F. and about 1700 F., withdrawing finely divided solid material comprising reduced metallic material from said first reaction zone and passing same to a second reaction zone, suspendingl said finely divided solid material in an upward owing oxygen-containing gas under conditions such that the reduced metallic material isoxidized, maintaining a temperature of reaction in said second reaction zone at least 200 F. above the temperature of reaction in said first reaction zone, removing finely divided solid material comprising oxidized metallic material from saidv second reaction zone and returning same to said rst reaction zone to supply oxygen for the oxidation of the methane therein, withdrawing from said first, reaction zone a gaseous eiiluent containinglhydrogen and an oxide of carbon and between about 0.001 and about 0.01 pound per cubic foot of gas of finely divided solid material comprising reduced metallic material, introducing. saidgaseous effluent containing said finelydivided solid material from said first reaction zone into a third reaction zone, maintaining the temperature of reaction in4 said third reaction zone between about 350 F. and about 750 F., removing finely divided solid material comprising metallic material from said third reactionizone and recycling same to said second reaction zone, removing from said third reaction zone a gaseous effluent comprising organic products of the process and separating same from said ellluent, maintaining an upward linear velocity of the gaseous streams` in the aforesaid reaction zones between aboutv 0.5 and about 6 feet per second under conditionsvsuch that the finely divided solid material isl suspended in the upward flowing gaseous stream in a pseudo-liquid fluidized condition whereby the finely divided solids achieve a highly turbulent condition in a pseudo-liquid dense phase, and maintaining the aforesaid reaction zones at substantially the same pressure between about atmospheric and about 500 pounds per square inch gage. s

6 A process for the synthesis of organic com.- pounds which comprises passing a methane-containing gas stream upward through a first. reaction zone in the presence of a finely divided solid material comprising, a reducible metaly oxide for thel hydrogenation. ,of carbon monoxideY pendedin said gaseous-mixture under conditions suchthat methane .is oxidized tocarbon monoxide andv hydrogen.. maintaining, atemperature of reaction in said rst reaction zone between about 1.100 andabout 1700F.', withdrawing finely divided solid material comprising reduced metallic materiall` Vfrom said first reaction zone and` passing same to a second reaction zone, suspendingl said finely divided solid material in an vlip-- ward owingfoxygen-containing gasun'der conditions: such tha'tthe reduced metallic materialis oxidized, maintaining a temperature-ofreaction in; said secondreaction zone at leastV 200 F. above' the temperatureof reactionfinsaid first reaction zone, removing nely divided solid material comprising oxidized metallic7 material from' saidsecond reaction' zonei andreturning same to said firstree action zonev to supply oxygen for theoxidationfo they methane therein, the Weight of' said finely divided. solid material circulated between. saidfrstf and said/secondreactiony zone being at least five times' the' weight theoretically required for sup'- plyingfoxygen for the oxidation of methane such that a major proportion of the heat reduired'in said first reaction zone is supplied from the sensible heat of the solid material circulated from said second reaction zone, withdrawingfrom said first reaction zone a gaseous eiiiuent containing carbon monoxide; hydrogen, and finely divided solid material comprisingreduced. metallic ma-il terial, introducing said gaseous efiiuent containing! said..neiy'divided solid material from said flrstireaction zone'. into a third reaction zone: in whichl hydrogen and carbon monoxide react/Ito produce organic compounds, suspending n'ely divided solid material in said thirdl reaction zone, maintaining the* temperature of reaction in said third reaction zone between about 350 F. and about 750 F.. removingI finely divided solid material comprising metallic material from said third. reaction zone 'andi recyciing same to said second reaction zone, removing from said third reactiony zone Aa gaseous eiiiuent comprising organic products-of the'processand separating same fromy said eiliuent, and maintaining a pressure within the aforesaid'reaction zones between about atmospheric and about 500 pounds per square inch gage.

'7. A process for thesynthesis of organic compoundsv'vliichi comprises passing a methane-containingl gas stream upward through a first reacl tion zone in the presence of finely dividedy solid materialcomprising a. reducible metal oxide which in its reducedY form is active as av catalyst lfor the hydrogenationv of an oxide of carbon suspended in said gaseous mixture under conditions such thatv methane is oxdizedto an oxide ofy carbon andihydrogen, maintaining a temperature of reaction" in said firstk reaction zone between about 500 F. and about 1700"` F., withdrawing nely divided solidmaterial comprising reduced metallic material' from said first reaction zone and passing saine to a'second reaction zone, suspending said finely, divided solidv material in an upward fiowing oxygen-containing gas under conditions such that the reduced metallic material is oxidized, removing finely divided solid material compris ing oxidized metallic material .from said second reaction zone andv returningV same to said first reactionzone tosupply oxygen for the oxidation of thelfinethane therein, withdrawing from'said firstr'eactonzme a gaseous efliuent containing Whig-11.111 its @duced foil, active satalyst y7,5 afndntra'ned atrasos divided solid material comprising reduced metallic material, passing said gaseous effluent and said entrained solid material from said first reaction zone to a third reaction zone in which the hydrogen and oxide of carbon products of said methane oxidation are reacted with each other, said gaseous effluent withdrawn from said first reaction zone and passed to said third reaction zone being substantially the sole source of the principal reactants to said third reaction zone, suspending finely divided solid material in a gas stream in said third reaction zone, removing finely divided solid material comprising metallic material from said third reaction zone and recycling same to said second reaction zone, removing from said third reaction zone a gaseous efiluent comprising organic products of the process, and maintaining a pressure within the aforesaid reaction zones between about atmospheric and about 500 pounds per square inch gage.

8. A process for the synthesis of organic compounds which comprises passing a methane-containing gas stream at a linear Velocity between about 0.5 and about 6 feet per second upward through a first reaction zone in the presence of a finely divided reducible metal oxide which in its reduced form is active as a catalyst for the hydrogenation of an oxide of carbon suspended in ak pseudo-liquid fiuidized condition in said ga'seous mixture under conditions such that methane is oxidized to produce hydrogen and an oxide of carbon,`maintaining a temperature of reaction in said first reaction zone between about 1100 F. and about 1700 F., withdrawing finely divided reduced metallic material from a pseudo-liquid phase of said first reaction zone and passing same to a second reaction zone, entraining said metallic material in an upward flowing oxygencontaining gas under conditions such that the reduced metallic material is oxidized, the linear velocity of said gas in said second reaction zone being about 6 feet per second and sufiicient to carry the entrained metallic material with the gas, maintaining a temperature of reaction in said second reaction zone between about 1600 F. and about 2000 F. and at least 200 F. above the temperature of reaction in said first reaction zone, withdrawing from said second reaction zone a gaseous efliuent containing entrained oxidized metallic material, removing finely divided oxidized metallic material from ysaid gaseous effluent from said second reaction zone and returning same to said first reaction zone to supply oxygen for the oxidation of the methane therein, withdrawing from said first reaction zone a gaseous effluent containing hydrogen and an oxide of carbon and nely divided reduced metallic material, introducing said gaseous effluent containing reduced metallic material from said first reaction zone into a third reaction zone in which the products of the oxidation of methane are converted to hydrocarbons and oxygenated organic compounds, maintaining in said third reaction zone `a temperature between about 350 F. and about 750 F., suspending finely divided metallic material in a fiuidized condition in said third reaction zone, removing finely divided metallic material from said third reaction zone and recycling same to said second reaction zone, removing from said third reaction zone a gaseous effluent comtaining a pressure within the aforesaid reaction zones between about atmospheric and about 500 pounds per square inch gagel 9. A process for the synthesis of organic coni-f pounds which comprises passing methane upward through a first reaction zone in the presence of a finely divided solid material comprising a reducible metal oxide which in its reduced form is active as a catalyst for thehydrogenation of an oxide of carbon suspended in said gaseous mixture under conditions such that methane is oxidized to produce hydrogen and an oxide of carbon, withdrawing yfinely divided solid material comprisingy reduced metallic material from `said first reaction zone and passing samel to a second reaction zone, in said second reaction zone sus# pending said iinelydivided solid material in an upward lfiowing gas comprising oxygen under conditions such that the reduced metallic material is oxidized, maintaining a temperature-of reaction in said second reaction zone at leastl 200 F. above the temperature vof reaction in said first reaction zone, removing finely divided solid material comprising oxidized metallic material from said sec-y ond reaction zone and returning same to said first reaction zone to supply oxygen for the oxidation of the methane therein, withdrawing from said first reaction zone a gaseous effluent containing hydrogen, an oxide of carbon and entrained finely divided solidmaterialcomprisin'g reduced metallic material, passing said gaseous effluent and said entrained finely divided solid material fromfsaid first reaction zone to` a third reaction zone, `insaid third reaction zone reacting the hydrogen and oxide of carbon products of said methane oxidation with each other, suspending `'finely divided solid material in a gasin said third reaction zone.,` removing finely' divided solid material from said third reaction zoneand recycling same to said second reaction zone, removing fromsaid third reaction zoneI a gaseous effluent comprising or-, ganic products of the process, and maintaining the pressure of said third reaction4 zone not higher than the pressure prevailing in the other reaction zones..

10. A process for the synthesis of organic compounds i which comprises passing methane through a first reaction zone in thepresence 4of a finely-divided'reducible metal oxide which` in its reduced form is active as a catalystu for the hydrogenation of an oxide of carbon suspended in said gaseous mixture under conditions such that methane is oxidized to produce hydrogen andan oxide of carbon,` withdrawing nely divided reduced metallic material from said first reaction zone and passing same to a second reaction zone.- suspending said finely divided material in flowing. oxygen under conditions such that the reduced metallic material is oxidized, removing finely divided oxidized metallic material from said sec.- ond reaction zone and returning same to saidy rst reaction zone to supply oxygen for the oxidation of the methane therein, withdrawing from said first reaction zone a gaseous effluent containing hydrogen, an oxide of carbon and entrained finely divided reduced-metallic material, passing said gaseous efIiuent and said entrained finely divided material from said first reaction zone to a third reaction zone` in which the hydrogen and oxide of carbon products of the methane oxidation are reacted with each other, suspending finely divided reduced metallic material in said third reaction zone, removing finely divided metallic material from said third reaction zone and recycling sarne to said second reaction zone. and removing from said third reaction zone a gaseous eilluent comprising organic products of als-vacas 2l! the process and separating same from said efnuent.

V11. A process Vfor the synthesis of organic compounds which comprises passing methane upward through a `first reaction zone in the presence of nelv divided `solid material comprising` a reducible metal oxide which Ain its reduced form is active as a catalvst for the hydrogenation of carbon monoxide suspended in said gas stream under conditions such that methane is converted to hydrogen and carbon monoxide, removing finely divided solid material comprising reduced metallic material from said rst reaction zone, suspending `said nnelydivlded solid material compricing reduced metallic material ina second reaction -zone with Yari-upward flowing oxygen-containing stream under conditions such that the reduced metallic material isoxidized to an oxide, removing finely divided solid material comprising a. metal oxide fromsaidsecondreaction-zone, introducing said iinely divided solid material from said. second reaction zone into said viirst reaction zoneto Vsupply oxygenr to ,the methane reaction therein, removing .a gaseous efliuent containing carbon monoxide, hydrogen, .and entr-ained finely divided solid material comprising reduced metallic material from said first reaction. zone, rapidly cooling. said reaction effluent fromsaid first reaction zone to atemneraturebelow about` '700 F., introducing the cooled reaction effluent into a scrubbing. .zonev scrubbing the `reaction effluent with #morsa-nic liould fraction comprisingv hvdrocarbone under conditionsr such that substantially all oi the entrained solid material is removed from the eflluent. compressing the scrubbed ellluent which is substantially free from finely divided solid material and Vpassing same to a third reaction zone, in said third reaction zone converting hydrogen and carbon monoxide to hydrocarbons,

oxygenated organic compounds, and water, re-

` loon monoxide in said third reaction Zone. removlns a. vaporous efllnentcomprisins hydrocarbons, water and oxvgenatedorsanic compounds from said third reaction zone, cooling and condensing Said. vaporous effluent to form ahvdrocarbon-rich liquid, phase and an aqueous-rich humid phase containing, oxysenated organic compounds, recovering oxysenated organic. compounds trom` said aquenis-richphasel as products of the process, re.- cl'llng substantially all of said hydrocarbon-rich liquid phase to the upper portion of saidy third reaction zone, removing an organic `liquid phase from the lower portion ofA said third reaction zone, cooling a portion of saidl organic liquid phase withdrawn from said third reaction zone and ne-V cycling same to the upper portion of said third reaction zone removing finely divided solid material from another `portion of said organic liquid phase from said third reaction zone, returning the recovered solid material to said second reaction zone, recovering organic liquid substantially ifree from solid material as a product of the process, maintaining a pressure in said rvst and second reaction zone below about `100 pounds per square inchy gage, vandl maintaining a pressure in said Athird reaction zonev between about 190 and. aboutoopoundsper square inch gage.

12. A process for the synthesis of organic compounds which comprises passing a methane-containing stream upward through a first reaction zone in the presenceof nely divided solid nia--V terial comprising a reducible metal oxide which nits reduced form is active as a catalyst for the hydrogenation of an oxide of carbon suspended in said gas stream under conditions such that methane is oxidized to hydrogen and an oxide of carbon, removing finely divided solid material comprising reduced metallic material froml said rst reaction zone, suspending said nely divided solid material comprising reduced metallic ma.-` terial in a second reaction zone with` an upward flowing oxygen-containing stream under condi-f tions such that the reduced metallic material es, oxidized to. an oxide, removing finely .vided Solid material comprising a metal oxide `from said. second reaction. zone. passing said nelvrdvided solid material comprising metal oxide from said second reaction zone to said first reaction zone-to supply oxygen to .the methane reaction therein. removing a gaseous effluent containing an oxide of carbon, hydrogen, and entrained nely divided solid material comprising reduced metallic materialfrom said first reaction zone, introducing the reaction eiiiuent into a scrubbing zone, scrubbing the reaction` eiliuent with an organic liquid fraction comprising hydrocarbons under condi.- tions such that substantially all of the entrained solid material is removed from the eiluent, com.. pressing the scrubbed eluent which is substan-Y tially free from finely divided solid material and passing same from said scrubbing zone to a third reaction zone, in said third reaction zone converting hydrogen and carbon monoxide to hydrocarbons and oxygenated organic compounds, removing from said scrubbing zone, a liquid orsanic scrubbing medium containing suspended solid material comprising reduced metallic ma.- terial removed from. said efliuent, passing said. scrubbing medium containing suspended solid material to said third reaction zone, maintaining intimate contact between organic liquid containing .suspended metallic material and hydrogen and an oxide o f carbon in said thirdreaction zone, removing a vaporous eflluent comprising hydrocarbons, water, and oxygenated organic compounds, cooling and condensing said vaporous effluent to form a hydrocarbon-rich liquid phase and an aqueous-rich liquid phase containing oxygenated organic compounds, recoving said oxygenated organic compounds from ysaid aqueousrich phase asv products of the, process, removing an organic liquid phase from the lower portion of said third reaction zone, removing nely divided solid material comprising reduced metallic material Vfrom said organic liquid phase from said third reaction zone, and returning the recovered solid material `to said second reaction zone, and recovering the liquid organic phase substantially free from solid material as a product of the process.

13. A process forthe synthesis o1 organicfcompounds which comprises passing methane through a iirst reaction zone in the presence of rlely` divided reducible lmetal oxide which in its reduced form is active as a catalyst for the hydrogenation of anoxide of carbon suspended in said methane under conditions such that methane is oxidized to produce hydrogen and an oxide of carbon, removing finely divided reduced metallic Vmaterial from said lrst reaction zone, suspending; saidV reduced metallic material in a second4 reaction zone in an upward lfdowillgA Stream comprising oxygen iinder conditions such that the reduced metallic material is oxidized, removingnely divided oxidized metallic material from said second reaction zone. introducing said finely divided solid material from said second reaction zone into said rst reaction zone to supply oxygen to the methane reaction therein, removing a gaseous eiuent containing entrained nely divided reduced metallic material from said iirst reaction zone, passing said gaseous eiiiuent and said entrained finely divided catalyst from said first reaction zone to a third reaction zone, in said third reaction zone converting the products of the methane oxidation to hydrocarbons and oxygenated organic compounds, maintaining intimatecontactbetween an organic liquid containing metallic material and the products of the methane oxidation in said third reaction zone, removing a vaporous eiiiuent comprising hydrocarbons, water, and oxygenated organic compounds from said third reaction zone, cooling and condensing said vaporous eliiuent to iorm a hydrocarbon-rich liquid phase and an aqueous-rich liquid phase containing oxygenated organic compounds, recovering oxygenated organic compounds from said aqueous-rich phase as products of the process, removing a liquid organic phase from the lower portion of said third reaction zone, removing finely divided solid material comprising reduced metallic material from said liquid organic phase from said third reaction zone, and returning the recovered solid material to said second reaction zone, and recovering the liquid organic phase substantially free from solid material as a product of the process.

" 14. The process of claim 'l in which said metal oxide comprises an oxide of copper.

15. A process for the synthesis of organic compounds which comprises passing a methane-containing gas stream upward through a first reaction zone in the presence of a finely-divided solid material comprising an iron oxide suspended in said gas stream under conditions such that methanek is oxidized to carbon monoxide and hydrogen, maintaining a temperature of 'reaction in said first reaction zone between about 1100" F. and about 1700D F., withdrawing iinely-divided solid material comprising reduced metallic material from said '.tlrst reaction zone and passing same to a second reaction zone, suspending said finely-divided solid material in an upward flowing `oxygen-containing gas under conditions such that the reduced metallic material is oxidized, maintaining a temperature of reaction in said second reaction zone atleast 200 F. above the temperature of reaction in said first reaction zone and not higher than about 2000o F., removing finely-divided solid material comprising oxidized `metallic material from said second reaction zone and returning same to said first reaction zone to Supply oxygen for the oxidation of the methane therein, the weight of said finely-divided solid material circulated between said ilrst and said second reaction zones being at leastvetimes the weight theoretically required for supplying' oxygen for the oxidation of methane such that a bon monoxide, hydrogen, and between about 0.001

and about 0.01 pound per cubic foot of gas of 'finely-divided solid material comprising reduced metallic material, introducing said gaseous ef- ;tiuent containing said finely-divided solid material from'saidnrst reaction zone intoa tliirdre-V action zone, in said third reaction zone reacting hydrogen and carbon monoxide to produce or-J ganic compounds, maintaining the temperature* of reaction in said third reaction zone between about 350' F. and about'750 F., removing finelydivided solid material comprising metallic material from said third reaction zone and recycling. same to said second reaction zone, removing from said third reaction zone a gaseous effluent comprising organic products of the process and separating same from said eiiluent, maintaining an upward linear velocity of the gaseous streams in the aforesaid reaction zones between about 0.5 andabout 6 feet per second under conditions such that the finely-divided solid material is suspended in the upward flowing gaseous stream in a pseudoliquid uidized condition whereby the nely-divided solids achieve a highly turbulent condition in a pseudo-liquid dense phase, and maintaining the aforesaid reaction zones at substantially the same pressurev between about atmospheric and abou 500 pounds per square inch gage. l

16. A process for the synthesis of organic compounds which comprises passing a methane-containing gas stream upward through a first reaction zone in the presence of a finely-divided solid material comprising an iron oxide suspended in said gasstream under conditions such that methane is oxidized to carbon monoxide and hydrogen, maintaining a temperature of reaction in said first reaction zone between about 1100 F. and about 1700" F., withdrawing finely-divided solid material comprising reduced metallic material from said first reaction zone and passing same to a second reaction zone, suspending said `finely-divided solid material in an upward flowing oxygen-containing gas under conditions such that the reduced metallic material is oxidized, maintaining a temperature of reaction in said second reaction zone between about 1200 F. and about 2000 F. and above the temperature of reaction in said first reaction zone, removing `finelydivided solid material comprising oxidized metallic material from said second reaction zone and returning same to said first reaction zone to supply oxygen for the oxidation of the methane therein, withdrawing from said first reaction zone a gaseous eilluent containing carbon monoxide, hydrogen, and between about 0.001 and about 0;01 pound per cubic foot of gasof finely-divided solid material comprising reduced metallic material, introducing said gaseous effluent containing said finely-divided solid material from said rst reaction zone into a third reaction zone, in said third reaction zone reacting hydrogen and carbon monoxide to produce organic compounds. maintaining the temperature of reaction in said third reaction zone between about 350 F. and about '150 F., removing finely-divided solid material comprising metallic material from said third reaction zone and recycling same to said second reactionrzone, removing from said third reaction zone Va-"gaseou's eiiluent comprising organic products of the process and separating same from said eiiiuent, maintaining an upward linear velocity of the gaseous streams in the aforesaid reaction zones between about 0.5 and about 6 feet per second under conditions such that the finely-divided solid material is suspended in the upward owing Igaseous stream in a pseudo-liquid iluidized condiamazes 20. The process of claim 19 in which a stripping gas is introduced into the conned passageway used for withdrawing finely-divided oxidized material from said second reaction zone in an amount to strip nitrogen from the withdrawn nely-divided solid material.

21. The process of claim 19 in which additional iinely-divided solid material is introduced directly from said first reaction zone into the conilned passageway containing the quenched effluent from said first reaction zone and in which a. vaporizable liquid is introduced into the eiliuent from said iirst reaction zone in an amount sufficient to cool the eiiluent and to aid in the passage of finely-divided solid material through the con- `fined passageway to said third reaction zone.

ARNOLD BELCHETZ.

REFERENCES CITED The following references are of record in the me oi this patent:

34 UNITED STATES PATENTS Number Name Date DeSimo Feb. 28, 1933 Duftschmid et al. May 23,1939 Peck June 13, 1939 Michaelvet al Dec. 12, 1939 Boyd et al Aug. 26, 1941 Gunness May 2, 1944 Roesch et al May 9, 1944 Johnson Jan. 29, 1946 Atwell Oct. 15, 1946 Sensel et al. Jan. 14, 1947"' Huber Mar. 11, 1947 Murphree et al Aug. 19, 1947 Johnson Dec. 17, 1948 Symonds Dec. 13, 1949 

10. A PROCESS FOR THE SYNTHESIS OF ORGANIC COMPOUNDS WHICH COMPRISES PASSING METHANE THROUGH A FIRST REACTION ZONE IN THE PRESENCE OF A FINELY DIVIDED REDUCIBLE METAL OXIDE WHICH IN ITS REDUCED FORM IS ACTIVE AS A CATALYST FOR THE HYDROGENATION OF AN OXIDE OF CARBON SUSPENDED IN SAID GASEOUS MIXTURE UNDER CONDITIONS SUCH THAT METHANE IS OXIDIZED TO PRODUCE HYDROGEN AND AN OXIDE OF CARBON, WITHDRAWING FINELY DIVIDED REDUCED METALLIC MATERIAL FROM SAID FIRST REACTION ZONE AND PASSING SAME TO A SECOND REACTION ZONE, SUSPENDING SAID FINELY DIVIDED MATERIAL IN FLOWING OXYGEN UNDER CONDITIONS SUCH THAT THE REDUCED METALLIC MATERIAL IS OXIDIZED, REMOVING FINELY DIVIDED OXIDIZED METALLIC MATERIAL FROM SAID SECOND REACTION ZONE AND RETURNING SAME TO SAID FIRST REACTION ZONE TO SUPPLY OXYGEN FOR THE OXIDATION OF THE METHANE THEREIN, WITHDRAWING FROM SAID FIRST REACTION ZONE A GASEOUS EFFLUENT CONTAINING HYDROGEN, AN OXIDE OF CARBON AND ENTRAINED FINELY DIVIDED REDUCED METALLIC MATERIAL, PASSING SAID GASEOUS EFFLUENT AND SAID ENTRAINED FINELY DIVIDED MATERIAL FROM SAID FIRST REACTION ZONE TO A THIRD REACTION ZONE IN WHICH THE HYDROGEN AND OXIDE OF CARBON PRODUCTS OF THE METHANE OXIDATION ARE REACTED WITH EACH OTHER, SUSPENDING FINELY DIVIDED REDUCED METALLIC MATERIAL IN SAID THIRD REACTION ZONE, REMOVING FINELY DIVIDED METALLIC MATERIAL FROM SAID THIRD REACTION ZONE AND RECYCLIC SAME TO SAID SECOND REACTION ZONE, AND REMOVING FROM SAID THIRD REACTION ZONE A GASEOUS EFFLUENT COMPRISING ORGANIC PRODUCTS OF THE PROCESS AND SEPARATING SAME FROM SAID EFFLUENT. 